[CANCER RESEARCH 46, 5482-5485, November 1986]
Selenium-induced Cytotoxicity of Human Leukemia Cells: Interaction
with Reduced Glutathione
Gerald Batist,1 Aspandiar G. Katki, Raymond W. Klecker, Jr., and Charles E. Myers
Clinical Pharmacology Branch, National Cancer Institute, Bethesda, Maryland 20892
ABSTRACT
Selenium exists in a number of forms with differing valence states,
some of which have shown antitumor activity. We studied the tumoricidal
activity of four currently available selenium forms against a human
leukemia cell line and exploited the differences among them to investigate
the mechanism of antitumor action. Only selenocystine and sodium
selenite showed antitumor activity, and these were also the only com
pounds which demonstrated significant redox chemistry, including deple
tion of cellular glutathione, stimulation of glutathione reductase, and
stimulation of oxygen consumption. The interaction of these two com
pounds with glutathione suggests an intriguing potential role for them in
cancer therapy.
INTRODUCTION
Selenium is an essential trace element in humans (1). Its only
established function is its presence in the enzyme glutathione
peroxidase (2). Using GSH2 as the reducing equivalent, this
enzyme plays a significant role in detoxification of peroxides
induced by oxygen radicals. As such it may be important in the
toxicity of anticancer treatments that generate such reactive
molecules (3). In addition, epidemiológica! and experimental
data suggest an anticarcinogenic activity by selenium (4).
Recent studies have also suggested an antineoplastic activity
by some forms of selenium, in particular the demonstration of
enhanced survival of Erlich ascites tumor-bearing mice treated
with selenite (5). ¡nvitro experiments with a variety of tumor
cell lines, mostly murine, have demonstrated growth inhibition
by some forms of selenium (6). In fact selenocystine was used
in the treatment of human leukemia in 1956 with some short-
term success (7). The mechanism of this effect was thought to
be competitive deprivation of cystine, but this was not proven.
Others have shown that selenium compounds can cause chro
mosome breaks and inhibit critical DNA synthetic enzymes (8,
9). Investigations in a variety of animal systems have suggested
that there is a significant interaction of selenium with glutathi
one independent of the enzyme glutathione peroxidase (10).
GSH is the major non-protein sulfhydryl and serves a number
of critical roles, particularly in oxidation-reduction reactions
(11). The cellular concentration of GSH has recently been
shown to affect significantly the efficacy and interactions of a
number of anticancer drugs (12, 13). We have examined the
cytotoxic effect of a number of selenium compounds on a
human leukemia cell line and investigated the interaction of
these compounds with intracellular GSH.
MATERIALS AND METHODS
Cells. The human promyelocytic leukemia cell line, HL-60, was a
kind gift of Dr. T. Breitman, National Cancer Institute. HL-60 cells
Received 1/8/86; revised 7/8/86; accepted 8/6/86.
The costs of publication of this article were defrayed in part by the payment
of page charges. This article must therefore be hereby marked advertisement in
accordance with 18 U.S.C. Section 1734 solely to indicate this fact.
1To whom requests for reprints should be addressed, at Montreal General
Hospital Research Institute, Room 960, U.S.C., 1650 Cedar Avenue, Montreal,
Quebec H3G 1A4, Canada.
2The abbreviations used are: GSH, reduced glutathione; PBS, phosphate
buffered saline; DMF, dose modifying factor; K \„. concentration resulting in
50% growth inhibition; GSSG, oxidized glutathione; GSSeSG, selenodigluta-
thione; GSSeH, selenopersulfide.
were grown continuously in RPMI 1640 medium supplemented with 2
HIMglutamine, 10% calf serum (Grand Island Biological Co., Grand
Island, NY), and penicillin-streptomycin (100 units/ml; 10 ml/liter),
under a 5% CO2 atmosphere. The cells were subcultured twice weekly.
For growth inhibition studies, 2 ml of cells at a density of 2.5 x 10s
cells/ml were plated into 6-well Linbro dishes in triplicate. Viability
was assessed by trypan dye exclusion, and cells were counted using a
Coulter Counter on the fourth day after cells were plated and exposed
to the drug.
Biochemical Studies. To assess the effect of selenium on reduced
glutathione and glutathione peroxidase activity, cells were incubated
for 24-h periods in the highest subcytotoxic dose for selenite (5 ^M)
and selenocystine (l UM),and at 100 MMfor each of selenomethionine
and seténate.
Reduced glutathione was measured using the fluorometric technique
of Hissin and Hilf (14), which takes advantage of the fact that the
fluorescent molecule ophthaldehyde selectively binds to reduced GSH
at pH 8. Cells were harvested after 24 h of exposure and were washed
twice in PBS and brought to a final concentration of at least 5 x 10'
cells/ml in 30 nM EDTA buffer. They were sonicated three times for
10 s on ice to achieve lysis. Twenty-five % of metaphosphoric acid was
added to precipitate the protein. After centrifugation, sodium phos
phate buffer (NaPO4), pH 9.0 was added to the supernatant to bring
the pH to 8. To 3 ml of this solution, 200 /tl of 1% ophthaldehyde
dissolved in methanol was added, and the reaction was permitted to
run for 15 min. Fluorescence was measured on a Perkin Elmer MPF-
44A fluorescence spectrophotometer with excitation at 350 and emis
sion at 420 nm. Standards were prepared fresh daily in NaPO«buffer
with 30 nM EDTA, pH 8.O.
Glutathione peroxidase was measured according to the technique of
Paglia and Valentine (15) using hydrogen peroxide, 0.25 HIM as sub
strate. After 24 h of exposure to the various selenium compounds, the
cells were washed twice in PBS and then resuspended in PBS diluted
1:1 with distilled water. After 10 min in this hypotonie solution, the
cells were subjected to homogenization three times for 10 s each on ice
using a Polytron homogenizer. Cell lysis was verified using phase
contrast microscopy. The cell homogenates were measured in triplicate.
NADPH oxidation induced by the various selenium compounds was
assessed by measuring the decreasing absorban«-at 340 nm over time
after addition of the selenium compound to a cuvet containing GSH
(0.25 mM), NADPH (0.25 HIM),and glutathione reductase (2 units). In
the absence of glutathione reductase there was no effect seen with any
of the selenium compounds, indicating that there was no nonenzymatic
NADPH oxidation.
Oxygraphic studies were performed at 37°Cin a Gilson Model 5/6
oxygraph apparatus equipped with a Clark type electrode (Yellow
Springs Instruments No. 5331). Each selenium compound to be tested
was dissolved in PBS. In the absence of GSH, there was no oxygen
consumption with any of the selenium compounds.
Chemicals. GSH and ophthaldehyde were from Sigma Chemical Co.,
St. Louis, MO; glutathione reductase was from Boehringer-Mannheim,
Inc., West Germany. The selenium compounds were prepared fresh for
each of the studies. Sodium selenite was obtained from ICN Nutritional
Biochemicals, Cleveland, OH; selenate was from ICN Pharmaceuticals,
Plainsview, NY; selenomethionine from Calbiochem-Behring, La Jolla,
CA; and selenocystine from Sigma. Selenocystine is the oxidized amino
acid cystine containing two selenium atoms/mol of selenocystine.
RESULTS
Only selenocystine and sodium selenite demonstrated signif
icant cytotoxic activity (Fig. 1). The IC50 for selenocystine is
5482
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